Rhodium-Catalyzed Cyclohydrocarbonylation:  Application to the Synthesis of (+)-Prosopinine and (−)-Deoxoprosophylline†

Iwao Ojima* and Ephraim S. Vidal
Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400
J. Org. Chem., 1998, 63 (22), pp 7999–8003
DOI: 10.1021/jo9815608
Publication Date (Web): October 9, 1998
Copyright © 1998 American Chemical Society
†

 This paper is dedicated to the late Dr. Maria Tzamarioudaki, a pioneer of cyclohydrocarbonylation processes, who lost her life in the Swissair flight 111 crash.

,
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

Abstract Image

Efficient convergent total syntheses of (+)-prosopinine (1) and (−)-deoxoprosophylline (4) were accomplished using Rh−BIPHEPHOS complex-catalyzed cyclohydrocarbonylation as the key step. The Rh−BIPHEPHOS complex-catalyzed cyclohydrocarbonylation of I, derived from (R)-serine, at 65 °C and 4 atm of CO and H2 (1:1) in ethanol afforded 6-ethoxypiperidine II, which was transformed to enantiopure (+)-prosopinine (1) in 3 steps. In a similar manner, (−)-deoxoprosophylline was synthesized through cyclohydrocarbonylation of IV derived from (S)-serine, giving 6-ethoxypiperidine V. The key intermediate V was transformed to enantiopure (−)-deoxoprosophylline (4) in 4 steps. These two short total syntheses clearly demonstrate the usefulness of the extremely regioselective cyclohydrocarbonylation process developed in these laboratories for the concise syntheses of piperidine alkaloids and related compounds.

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History

  • Published In Issue October 30, 1998
  • Received August 3, 1998

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